• 펄프종이기술
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• 제47권2호
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• pp.42-52
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• 2015

In this study, cellulose nanofibrils (CNF) were modified through carboxymethylation or TEMPO-mediated oxidation and their effects on ionicity and characteristics of sheet, film, and foam were investigated. Carboxymethylation was carried out on pulp fibers as a pre-treatment before preparation of CNF. The gel-like and translucent CNF hydrogel was obtained by grinding of carboxymethylated cellulose fibers. Carboxymethylated CNF film and freeze dried sheet showed higher transparency than that of untreated CNF. The CNF sheet with high strength and the CNF foam without large ice crystals were obtained by using the carboxymethylated CNF. TEMPO-mediated oxidation was carried out as a post-treatment of CNF. The zeta potential and charge demand of TEMPO-oxidized CNF were increased with an increase in oxidation time and addition amount of NaClO. The density of sheet made of TEMPO oxidized CNF was increased with the amount of oxidizing agent. The TEMPO oxidized cellulose nanofiber (TOCN) which was obtained from supernatant after centrifugation could be converted to transparent film.

• Journal of the Korean Wood Science and Technology
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• 제43권5호
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• pp.613-627
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• 2015

Simple methods of conductometric titration and infrared spectroscopy were used to quantify the surface carboxyl content of cellulose fibrils isolated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. The effects of different cellulose sources, post or assisted-sonication oxidation treatment, and the amount of sodium hypochlorite addition on the carboxyl content of cellulose were reported. This study showed that post sonication treatment had no influence on the improvement of surface carboxyl charge of cellulose macrofibrils (CMFs). However, the carboxyl content increased for the isolated cellulose nanofibrils (CNFs). Thus the carboxyl content of CNFs is different from those of their corresponding bulk oxidized cellulose and CMFs. Filter paper as a CNF source imparted a higher surface charge than did hardwood bleached kraft pulp (HWBKP) and microcrystalline cellulose (MCC). It was considered that the crystallinity and microstructure of the initial cellulose affected oxidation efficiency. In addition, the carboxyl content of cellulose was successfully controlled by applying sonication treatment during the oxidation reaction and adjusting the amount of sodium hypochlorite.

• 대한화학회지
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• 제39권8호
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• pp.657-665
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• 1995

여러가지 비대칭 벤질 에테르들과 벤질 알킬 에테르들을 $CH_3CO_2Et$-NaOCI수용액(6.6 mol eq.)의 2상 용매계에서 4-methoxy-2, 2, 6, 6,-tetramethylpiperidine-1-oxyl(0.03 mol eq., 4-methoxy-TEMPO)을 이용하여 산화시키면 벤조에이트로 산화가 일어난다. 4-methoxy-TEMPO는 2차 산화제인 NaOCI에 의하여 본반응의 산화제인 N-oxo-4-2, 2, 6, 6, -tetramethyl-piperidium 염(N-oxoammonium 염)으로 변환된다. N-oxoammonium 염은 에테르를 산화시키고 N-hydroxy-4-methoxy-2, 2, 6, 6,-tetramethylpiperidine(hydroxyamine)으로 환원된다. Hydroxy-amine은 NaOCI에 의하여 N-oxoammonium 염으로 순환 재생되므로 4-methoxy-TEMPO는 촉매량 사용하였다. 이 반응은 또한 조촉매인 KBr(0.03 mol eq.)가 필수적이고 반응 중 pH는 8.0 이하로 유지되어야 한다. 0 - 5$^{\circ}C$의 반응 온도로 2.5시간 반응시키면 대부분 벤조에이트로 산화 되었다. 벤질 알킬 에테르들의 선택성 산화는 수소의 산도와 알킬기의 입체효과에 영향을 받음이 고찰되었다.

• Journal of the Korean Wood Science and Technology
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• 제42권2호
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• pp.119-129
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• 2014

This work undertook to prepare nanofibers of cellulose nanofibrils (CNF)/polyvinyl alcohol (PVA) composite by electrospinning, and characterize the electrospun composite nanofibers. Different contents of CNFs isolated from hardwood bleached kraft pulp (HW-BKP) by 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation were suspended in aqueous polyvinyl alcohol (PVA) solution, and then electrospun into CNF/PVA composite nanofibers. The morphology and dimension of CNFs were characterized by transmission electron microscopy (TEM), which revealed that CNFs were fibrillated form with the diameter of about $7.07{\pm}0.99$ nm. Morphology of the electrospun nanofiber observed by field-emission scanning electron microscopy (FE-SEM) showed that uniform CNF/PVA composite nanofibers were manufactured at 1~3% CNF contents while many beads were observed at 5% CNF level. Both the viscosity of CNF/PVA solution and diameter of the electrospun nanofiber decreased with an increase in CNF content. The diameter and its distribution of the electrospun nanofibers helped explain the differences observed in their morphology. These results show that the electrospinning method was successful in preparing uniform CNF/PVA nanofibers, indicating a great potential for manufacturing consistent and reliable cellulose-based nanofibrils for scaffolds in future applications.

• Current Research on Agriculture and Life Sciences
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• 제31권1호
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• pp.18-24
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• 2013

This work attempted to fabricate organic/inorganic nanocomposite by combining organic cellulose nanofibrils (CNFs), isolated by 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation of native cellulose with inorganic nanoclay. The morphology and dimension of CNFs, and tensile properties and thermal stability of CNF/clay nanocomposites were characterized by transmission electron microscope (TEM), tensile test, and thermogravimetry (TG), respectively. TEM observation showed that CNFs were fibrillated structure with a diameter of about $4.86{\pm}1.341nm$. Tensile strength and modulus of the hybrid nanocomposite decreased as the clay content of the nanocomposite increased, indicating a poor dispersion of CNFs or inefficient stress transfer between the CNFs and clay. The elongation at break increased at 1% clay level and then continuously decreased as the clay content increased, suggesting increased brittleness. Analysis of TG and derivative thermogravimetry (DTG) curves of the nanocomposites identified two thermal degradation peak temperatures ($T_{p1}$ and $T_{p2}$), which suggested thermal decomposition of the nanocomposites to be a two steps-process. We think that $T_{p1}$ values from $219.6^{\circ}C$ to $235^{\circ}C$ resulted from the sodium carboxylate groups in the CNFs, and that $T_{p2}$ values from $267^{\circ}C$ to $273.5^{\circ}C$ were mainly responsible for the thermal decomposition of crystalline cellulose in the nanocomposite. An increase in the clay level of the CNF/clay nanocomposite predominately affected $T_{p2}$ values, which continuously increased as the clay content increased. These results indicate that the addition of clay improved thermal stability of the CNF/clay nanocomposite but at the expense of nanocomposite's tensile properties.

• Current Research on Agriculture and Life Sciences
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• 제31권4호
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• pp.250-255
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• 2013

As a renewable nanomaterial, cellulose nanocrystal (CNC) isolated from wood grants excellent mechanical properties in developing high performance nanocomposites. This study was undertaken to compare the reinforcing efficiency of two different CNCs, i.e., cellulose nanowhiskers (CNWs) and cellulose nanofibrils (CNFs) from hardwood bleached kraft pulp (HW-BKP) as reinforcing agent in polyvinyl alcohol (PVA)-based nanocomposite. The CNWs were isolated by sulfuric acid hydrolysis while the CNFs were isolated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. Based on measurements using transmission electron microscopy, the individual CNWs were about $6.96{\pm}0.87nm$ wide and $178{\pm}55nm$ long, while CNFs were $7.07{\pm}0.99nm$ wide. The incorporation of CNWs and CNFs into the PVA matrix at 5% and 1% levels, respectively, resulted in the maximum tensile strength, indicating different efficiencies of these CNCs in the nanocomposites. Therefore, these results suggest a relationship between the reinforcing potential of CNCs and their physical characteristics, such as their morphology, dimensions, and aspect ratio.